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Photochemistry

PQ and water oxy-trifluoromethylate enynes

Jana S, Verma A, Kadu R, et al. · Chemical science · 2017

Open access · cc by · source: Europe PMC

Sunlight-excited phenanthrenequinone turns Langlois’ CF3SO2Na into CF3· and uses water as the oxygen atom to build CF3 benzofurans, benzothiophenes and indoles.

Key findings

PQ in CH3CN/water under sunlight (or 23 W CFL) gives benzofurans 57–75%, benzothiophenes 73–36%, N-Ts indoles 67–56%. 18O lands in the ketone (m/z 307.0821). H2 (δ 4.57 ppm) and H–D from D2O evolve. EPR sextet of tBu(CF3)NO·; φ = 27 implies a chain. DFT hydration barrier +16.47 kcal mol–1.

Methodology

Authors screened diketones/oxidants on phenolic 1,6-enynes, then mapped O-, S- and N-linked substrates, 18O-water labelling, EPR spin trapping, CV of PQ, and B3LYP hydration barriers.

Limitations

Alkyl-substituted enynes give low yields; Boc-indoles can drop to 10%; H2 is inferred from NMR not quantified gas chromatography; chain carrier HSO2· is proposed, not isolated.

How this study connects

Role on claims

Each row is a claim on a concept or method page where this paper supports, challenges, or qualifies the statement. Roles are hand-checked — not a model guess.

  • SupportsCyclic Voltammetrymethod

    CV also appears as a supporting characterisation of materials and mechanisms: pore-confined Pt–Ni ORR, a stibnite/carbon sodium-ion composite, and a photoredox trifluoromethylation where CV of 9,10-phenanthrenequinone sits beside EPR and ¹⁸O labelling. Those papers are not primarily about teaching CV, but they still use a voltammogram as evidence.

    Evidence for the claim as stated.

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